Filter dyes for photographic elements

ABSTRACT

Solid particle dispersions of dyes according to the formula:    &lt;IMAGE&gt;  (I)  wherein D is selected from the group consisting of   &lt;IMAGE&gt;    &lt;IMAGE&gt;   and ketomethylene nuclei are disclosed as filter dyes for photographic elements. In this formula, E1 and E2 are each independently electron withdrawing groups. R1 and R6 are each independently R or NHR, where R is aryl. R2 and R3 are each independently alkyl or aryl, or represent the carbon atoms necessary to form a fused ring with the phenyl ring to which the N atom is attached. R4 and R7 are each independently hydrogen, alkyl or aryl. R5 is alkyl. Z represents the atoms necessary to complete a 5 or 6 memebered heterocyclic nucleus. M+ is a cation. L1 through L7 are each independently methine groups. m is 0, 1, 2, or 3. n is 0 or 1. p is 0, 1, 2, 3, or 4. q is 0, 1, 2, or 3. At least one of R1 or D includes an aryl ring substituted with a carboxy or sulfonamido substituent.

This is a divisional of application Ser. No. 733,929, filed Jul. 22,1991, now U.S. Pat. No. 5,213,956.

This invention relates to dyes, particularly dyes useful as filter dyes,especially in photographic elements.

Photographic materials often contain filter dyes to absorb light fromdifferent regions of the spectrum, such as red, blue, green,ultraviolet, and infrared, to name a few. These filter dyes are oftenrequired to perform the function of absorbing light during exposure ofthe material so as to prevent or at least inhibit light of a region ofthe spectrum from reaching at least one of the radiation-sensitivelayers of the element.

After processing of the element, however, the continued presence of thefilter dye will adversely affect the image quality of the photographicmaterial. It is therefore desirable to use filter dyes that will besolubilized and removed or at least decolorized during photographicprocessing. Dyes that are easily solubilized, however, tend to wanderthroughout the photographic material during coating, adversely affectingthe final image quality.

To prevent dye wandering, the dyes are often coated with a mordant tobind the dye in the layer in which it is coated. Dye mordants, whileoften useful, tend to either bind the dye too strongly, inhibitingsolubilization of the dye during photographic processing, or too weakly,thus not preventing dye wandering.

It would therefore be highly desirable to provide a filter dye for usein photographic elements that does not wander during coating withoutrequiring a mordant, and which is fully solubilized during processingfor decolorizing and/or removal. It would be further desirable toprovide filter dyes which in addition to the above also exhibit highcovering power such that lower amounts of dye can be used, which wouldbe advantageous for environmental concerns.

U.S. Pat. Nos. 4,950,586, 4,948,718, 4,948,717, 4,940,654, 4,923,788,4,900,653, 4,861,700, 4,857,446, and 4,855,221 disclose the use ofvarious dyes in solid particle dispersions. These patents disclose thatthe use of solid particle dye dispersions allows for the coating offilter dyes which are immobile in coated acidic emulsion layers yetwhich can be fully removed during basic aqueous film or paperprocessing. The specific dyes of the present invention are notdisclosed.

U.S. Pat. Nos. 2,926,187 and 4,952,553, Japanese Kokai Nos. 61-281156,61-103862, and 60-226555, and L. Hennig et al., Z. Chem., 29, 168 (1989)disclose dyes similar to those of the present invention. The specificdyes of the invention are not disclosed, however, and there is nosuggestion of the use of such dyes in silver halide photographicelements.

According to the invention, there is provided a photographic elementhaving a layer comprising a hydrophilic binder and, as a filter dye, asolid particle dispersion of a compound having the formula: ##STR3##wherein: D is selected from the group consisting of ##STR4## andketomethylene nuclei; E¹ and E² are each independently electronwithdrawing groups;

R¹ and R⁶ are each independently R or NHR, where R is substituted orunsubstituted aryl;

R² ahd R³ are each independently substituted or unsubstituted alkyl orsubstituted or unsubstituted aryl, or represent the carbon atomsnecessary to form a fused ring with the phenyl ring to which the N atomis attached;

R⁴ and R⁷ are each independently hydrogen, substituted or unsubstitutedalkyl or substituted or unsubstituted aryl;

R⁵ is substituted or unsubstituted alkyl;

Z represents the atoms necessary to complete a substituted orunsubstituted 5 or 6 memebered heterocyclic nucleus;

M⁺ is a cation;

L¹ through L⁷ are each independently substituted or unsubstitutedmethine groups;

m is 0, 1, 2, or 3; n is 0 or 1; p is 0, 1, 2, 3, or 4; q is 0, 1, 2, or3;

at least one of R¹ or D comprising an aryl ring substituted with acarboxy or sulfonamido substituent.

Solid particle dispersions of the compound of formula (I) are useful asgeneral purpose filter dyes, alone or in combination with other filterdyes in photographic elements. They are insoluble at coating pH's of 6or less (generally 4 to 6) and soluble at processing pH's of 8 or more(generally 8 to 12), so that they do not interact with other componentsof the photographic element, yet still are fully solubilized duringphotographic processing.

A particular advantage of the dyes of the invention is that they providehigher covering power at their coating λmax than comparable known solidparticle dispersion dyes. This advantage is particularly important inmodern film formats and processing conditions, as filter dyes with ahigh covering power need not be coated at as high a coverage as dyeswith lower covering power in order to achieve the same degree of lightfiltration. In addition to reducing manufacturing costs, lower levels ofcoated dyes will reduce the level of organic dye build up in processingsolutions, and the resulting lower levels of dissolved dyes removed fromprocessed photographic elements will have a reduced environmentalimpact.

A further advantage of dyes of the invention is that they generallypossess deeper λmax values than comparable known filter dyes. This maybe particularly advantageous where dyes absorbing infrared light aredesired.

According to formula (I), E¹ and E² are each electron withdrawinggroups. Electron withdrawing groups in organic compounds are well-knownin the art, such as described in J. Marsh, Advanced Organic Chemistry,3rd Ed., p.238, the disclosure of which is incorporated herein byreference in its entirety Examples of such groups include cyano, acyl,aminocarbonyl, and alkoxycarbonyl. In a preferred embodiment, E¹ and E²are cyano.

R² and R³ can be substituted or unsubstituted alkyl or substituted orunsubstituted aryl. Preferably, these groups are each independentlysubstituted or unsubstituted alkyl of 1 to 6 carbon atoms or substitutedor unsubstituted aryl of 6 to 14 carbon atoms. The alkyl or aryl groupmay be substituted with any of a number of substituents as is known inthe art, other than those, such as sulfo substituents, that would tendto increase the solubility of the dye so much as to cause it to becomesoluble at coating pH's. Examples of useful substituents includehalogen, alkoxy, ester groups, amido, acyl, alkylamino, carboxy, andsulfonamido. Examples of alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, or isohexyl. Examplesof aryl groups include phenyl, naphthyl, anthracenyl, pyridyl, andstyryl.

R can be substituted or unsubstituted aryl, preferably of from 6 to 14carbon atoms. Examples of aryl groups include phenyl, naphthyl,anthracenyl, pyridyl, and styryl. Useful substituents include thoselisted above for R² and R³.

R⁴ and R⁷ are each independently hydrogen, substituted or unsubstitutedalkyl, preferably from 1 to 6 carbon atoms, or substituted orunsubstituted aryl, preferably from 6 to 14 carbon atoms. Examples of R⁴and R⁷ include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, tolyl,and phenyl. Useful substituents include those listed above for R² andR³.

R⁵ is substituted or unsubtituted alkyl, preferably of from 1 to 15carbon atoms. Examples of R⁵ include methyl, ethyl, propyl,methoxyethyl, benzyl, and carboxybenzyl. Additional useful substituentsinclude those listed above for R² and R³.

Z represents the atoms necessary to complete a substituted orunsubstituted 5 or 6 membered heterocyclic nucleus. The heterocyclicnucleus is of the type commonly used in cyanine dyes, and is well-knownin the art. They are described, for example, in "The Cyanine Dyes andRelated Compounds", Frances Hamer, Interscience Publishers, 1964, thedisclosure of which is incorporated by reference. Examples of suchheterocyclic nuclei include thiazole, selenazole, oxazole, imidazole,indole, benzothiazole, benzoselenazole, benzoxazole, benzimidazole,benzindole, naphthothiazole, naphthoselenazole, naphthoxazole, andnaphthimidazole. The nucleus may be substituted with known substituents,such as substituted or unsubstituted alkyl of from 1 to 10 carbon atoms(e.g., methyl, ethyl, 3-chloropropyl), alkoxy of from 1 to 8 carbonatoms (e.g., methoxy, ethoxy), halogen (e.g., chloro, fluoro),substituted or unsubstituted aryl of from 6 to 20 carbon atoms (e.g.,phenyl), or with carbon atoms forming a fused ring system (e.g. in abenzothiazole or a naphthothiazole nucleus). In a preferred embodiment,z represents the atoms necessary to complete a substituted orunsubstituted benzoxazole nucleus.

M⁺ is a cation such as Et₃ NH+, Na⁺, K⁺.

Ketomethylene nuclei are a well-known class of chemical groups asdescribed, for example, in the above referenced Hamer, The Cyanine Dyesand Related Compounds, pp. 469-494, 595-604 (1964). Examples ofpreferred ketomethylene residues include benzoyl acetonitrile,2-pyrazolin-5-one, pyrazolindione, barbituric acid nuclei, rhodanine,indanedione, isoxazolinone, benzofuranone, chromandione,cyclohexanedione, dioxanedione, furanone, isoxazolidindione, pyrandione,and pyrrolinone.

L¹ through L⁷ are substituted or unsubstituted methine groups, e.g.--CR⁸═ groups, where R⁸ represents hydrogen or substituted or unsubstitutedalkyl or substituted or unsubstituted aryl as described above for R² andR³.

Dyes of formula I include at least one carboxy or sulfonamidosubstituent. Carboxy groups have the formula--CO₂ H and sulfonamidogroups have the formula--NHSO₂ R⁹ where R⁹ is substituted orunsubstituted alkyl or substituted or unsubstituted aryl as describedabove for R² and R³.

Examples of dyes according to formula (I) include the following:

    __________________________________________________________________________    1-4)                                                                               ##STR5##                                                                 Dye R.sub.1                         m  Solution λ-max                                                                   ε(×                                                             10.sup.4)                    __________________________________________________________________________    1   NHSO.sub.2 CH.sub.3             0  514.sup.a 5.20                         2   CO.sub.2 H                      0  517.sup.b 4.56                         3   NHSO.sub.2 CH.sub.3             0  590.sup.a 5.93                         4   CO.sub.2 H                      0  608.sup.a 6.60                         __________________________________________________________________________    5-8)                                                                               ##STR6##                                                                                                        Solution λ-max nm               Dye R.sub.1, R.sub.2                m  (MeOH)    ε(×                                                             10.sup.4)                    __________________________________________________________________________    5   NHSO.sub.2 CH.sub.3             0  509       7.20                         6   CO.sub.2 H                      0  505       6.63                         7   CO.sub.2 H                      1  615       14.3                         8   NHSO.sub.2 CH.sub.3             1  616       10.1                         __________________________________________________________________________    9)                                                                                 ##STR7##                          Solution λ-max 384 nm                                                  (MeOH)    ε = 2.68 ×                                                      10.sup.4                     10)                                                                                ##STR8##                          Solution λ-max 450 nm                                                  (MeOH)                                 11)                                                                                ##STR9##                          Solution λ-max 584 nm                                                  (acetone) ε = 5.89 ×                                                      10.sup.4                     __________________________________________________________________________    12-27)                                                                             ##STR10##                                                                                                       Solution λ-max nm               Dye R.sub.1    R.sub.2   R.sub.3    m  (MeOH)                                 __________________________________________________________________________    12  H          C.sub.2 H.sub.5                                                                         NHSO.sub.2 CH.sub.3                                                                      0  492                                    13  H          C.sub.2 H.sub.5                                                                         NHSO.sub.2 CH.sub.3                                                                      1  598                                    14  H          4-carboxy benzyl                                                                        H          0  497*                                   15  H          4-carboxy benzyl                                                                        H          1  595                                    16  H          CH.sub.3  CO.sub.2 H 0  495                                    17  H          CH.sub.3  CO.sub.2 H 1  592                                    18  NHSO.sub.2 CH.sub.3                                                                      C.sub.2 H.sub.5                                                                         H          0  495                                    19  NHSO.sub.2 CH.sub.3                                                                      C.sub.2 H.sub.5                                                                         H          1  594                                    20  NHSO.sub.2 CH.sub.3                                                                      CH.sub.3  NHSO.sub.2 CH.sub.3                                                                      0  494                                    21  NHSO.sub.2 CH.sub.3                                                                      CH.sub.3  NHSO.sub.2 CH.sub.3                                                                      1  604                                    22  NHSO.sub.2 CH.sub.3                                                                      CH.sub.3  CO.sub.2 H 0  496                                    23  NHSO.sub.2 CH.sub.3                                                                      CH.sub.3  CO.sub.2 H 1  595                                    24  CO.sub.2 H CH.sub.3  CO.sub.2 H 0  495                                    25  CO.sub.2 H C.sub.2 H.sub.5                                                                         H          1  578                                    26  CO.sub.2 H 4-carboxy benzyl                                                                        H          1  594                                    27  NHSO.sub.2 CH.sub.3                                                                      4-carboxy benzyl                                                                        H          1  598                                    __________________________________________________________________________    28)                                                                                ##STR11##                                                                29)                                                                                ##STR12##                                                                30)                                                                                ##STR13##                                                                31)                                                                                ##STR14##                                                                32)                                                                                ##STR15##                                                                33)                                                                                ##STR16##                                                                34)                                                                                ##STR17##                                                                35)                                                                                ##STR18##                                                                36)                                                                                ##STR19##                                                                37)                                                                                ##STR20##                                                                38)                                                                                ##STR21##                                                                39)                                                                                ##STR22##                                                                40)                                                                                ##STR23##                                                                41)                                                                                ##STR24##                                                                42)                                                                                ##STR25##                                                                43)                                                                                ##STR26##                                                                44)                                                                                ##STR27##                                                                45)                                                                                ##STR28##                                                                46)                                                                                ##STR29##                                                                47)                                                                                ##STR30##                                                                48)                                                                                ##STR31##                                                                49)                                                                                ##STR32##                                                                50)                                                                                ##STR33##                                                                51)                                                                                ##STR34##                         Solution (MeOH) λmax 720                                               nm                                     52)                                                                                ##STR35##                         Solution (MeOH) λmax 838                                               nm                                     53)                                                                                ##STR36##                         Solution (MeOH) λmax 570                                               nm                                     54)                                                                                ##STR37##                         Solution (MeOH) λmax 568                                               nm                                     55)                                                                                ##STR38##                         Solution (MeOH) λmax 553                                               nm                                     56)                                                                                ##STR39##                         Solution (MeOH) λmax 552        __________________________________________________________________________                                           nm                                      .sup.a (CH.sub.3 CN)                                                          .sup.b (MeOH + Et.sub.3 N)                                                    *MeOH + Et.sub.3 N solution                                              

The dyes of formula (I) can be prepared by synthetic techniqueswell-known in the art, as illustrated by the synthetic examples below.Such techniques are further illustrated, for example, in "The CyanineDyes and Related Compounds", Frances Hamer, Interscience Publishers,1964.

The dyes of formula (I) may be incorporated in a hydrophilic layer of aphotographic element in any known way (e.g., with the aid of ahigh-boiling non-polar organic solvent), but are preferably in the formof a solid particle dispersion (i.e., the dye is in the form of solidparticles of microscopic size) for incorporation into a layer such as ahydrophilic colloid layer of a photographic element. The solid particledispersion can be formed by precipitating the dye in the form of adispersion and/or by well-known milling techniques, e.g., ball-milling,sand-milling, or colloid-milling (preferably ball-milling orsand-milling) the dye in the presence of a dispersing agent. Thedispersion of dye particles should have a mean diameter of less than 10μm and preferably less than 1 μm. The dye particles can be prepared insizes ranging down to about 0.01 μm.

The dyes may be located in any layer of the element where it isdesirable to absorb light, but it is particularly advantageous to locatethem in a layer where they will be solubilized and washed out duringprocessing. Useful amounts of dye range from 1 to 1000 mg/m² The dyeshould be present in an amount sufficient to yield an optical density atthe absorbance D-max in the visible region before processing of at least0.10 density units and preferably at least 0.50 density units. Thisoptical density will generally be less than 5.0 density units for mostphotographic applications.

The hydrophilic binder used in the present invention can be any knowntype, such as a hydrophilic colloid (e.g., gelatin), polyvinyl alcohol,and the like, as are well-known in the art.

The support of the element of the invention can be any of a number ofwell-known supports for photographic elements. These include polymericfilms such as cellulose esters (e.g., cellulose triacetate anddiacetate) and polyesters of dibasic aromatic carboxylic acids withdivalent alcohols (e.g., poly(ethylene terephthalate)), paper, andpolymer-coated paper. Such supports are described in further detail inResearch Disclosure, December, 1978, Item 17643 [hereinafter referred toas Research Disclosure], Section XVII.

The radiation-sensitive layer of the element of the invention cancontain any of the known radiation-sensitive materials, such as silverhalide, diazo image-forming systems, light-sensitivetellurium-containing compounds, light-sensitive cobalt-containingcompounds, and others described in, for example, J. Kosar,Light-Sensitive Systems: Chemistry and Application of Nonsilver HalidePhotographic Processes, J. Wiley & Sons, N.Y. (1965).

Silver halide is especially preferred as a radiation-sensitive material.Silver halide emulsions can contain, for example, silver bromide, silverchloride, silver iodide, silver chlorobromide, silver chloroiodide,silver bromoiodide, or mixtures thereof. The emulsions can includecoarse, medium, or fine silver halide grains bounded by 100, 111, or 110crystal planes. Silver halide emulsions and their preparation arefurther described in Research Disclosure, Section I. Also useful aretabular grain silver halide emulsions, as described in ResearchDisclosure, January, 1983, Item 22534 and U.S. Pat. No. 4,425,426.

The radiation-sensitive materials described above can be sensitized to aparticular wavelength range of radiation, such as the red, blue, orgreen portions of the visible spectrum, or to other wavelength ranges,such as ultraviolet, infrared, and the like. Sensitization of silverhalide can be accomplished with chemical sensitizers such as goldcompounds, iridium compounds, or other group VIII metal compounds, orwith spectral sensitizing dyes such as cyanine dyes, merocyanine dyes,styryls, or other known spectral sensitizers. Additional information onsensitization of silver halide is described in Research Disclosure,Sections I-IV.

The dyes of the invention can be used as interlayer dyes, trimmer dyes,or antihalation dyes. They can be used to prevent crossover in X-raymaterials as disclosed in U.S. Pat. Nos. 4,900,652 and 4,803,150 andEuropean Patent Application Publication No. 0 391 405, to preventunwanted light from reaching a sensitive emulsion layer of a multicolorphotographic element as disclosed in U.S. Pat No. 4,988,611, and forother uses as indicated by the absorbance spectrum of the particulardye. The dyes can be used in a separate filter layer or as an intergrainabsorber.

Multicolor photographic elements according to the invention generallycomprise a blue-sensitive silver halide layer having a yellowcolor-forming coupler associated therewith, a green-sensitive layerhaving a magenta color-forming coupler associated therewith, and ared-sensitive silver halide layer having a cyan color-forming couplerassociated therewith. Color photographic elements and color-formingcouplers are well-known in the art and are further described in ResearchDisclosure, Section VII.

The element of the invention can also include any of a number of otherwell-known additives and layers, as described in Research Disclosure.These include, for example, optical brighteners, antifoggants, imagestabilizers, light-absorbing materials such as filter layers orintergrain absorbers, light-scattering materials, gelatin hardeners,coating aids and various surfactants, overcoat layers, interlayers andbarrier layers, antistatic layers, plasticizers and lubricants, mattingagents, development inhibitor-releasing couplers, bleachaccelerator-releasing couplers, and other additives and layers known inthe art.

The dye of formula (I) can be located in any layer of a photographicelement where it is desired to absorb light. In a preferred embodiment,the dye is preferably located in a layer where it will be subjected tohigh pH (i.e., 8 to 12) and/or sulfite during photographic processing,so as to allow the dye to be solubilized and removed or decolorized .

The photographic elements of the invention, when exposed, can beprocessed to yield an image. During processing, the dye of formula (I)will generally be decolorized and/or removed. Following processing, thedye of the invention should contribute less than 0.10 density unit, andpreferably less than 0.02 density unit to the absorbance D-max in thevisible region in the minimum density areas of the exposed and processedelement.

Processing can be by any type of known photographic processing, asdescribed in Research Disclosure, Sections XIX-XXIV, although itpreferably includes a high pH (i.e., 8 or above) step utilizing anaqueous sulfite solution in order to maximize decolorization and removalof the dye. A negative image can be developed by color development witha chromogenic developing agent followed by bleaching and fixing. Apositive image can be developed by first developing with anon-chromogenic developer, then uniformly fogging the element, and thendeveloping with a chromogenic developer. If the material does notcontain a color-forming coupler compound, dye images can be produced byincorporating a coupler in the developer solutions.

Bleaching and fixing can be performed with any of the materials known tobe used for that purpose. Bleach baths generally comprise an aqueoussolution of an oxidizing agent such as water soluble salts and complexesof iron (III) (e.g., potassium ferricyanide, ferric chloride, ammoniumof potassium salts of ferric ethylenediaminetetraacetic acid),water-soluble persulfates (e.g., potassium, sodium, or ammoniumpersulfate), water-soluble dichromates (e.g., potassium, sodium, andlithium dichromate), and the like. Fixing baths generally comprise anaqueous solution of compounds that form soluble salts with silver ions,such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate,sodium thiocyanate, thiourea, and the like.

The invention is further illustrated by the following Examples.

Synthesis of 2-(4-methylsulfonamido)phenyl-1,1,3-tricyanopropene:

A slurry of 59.0 grams (0.248 mol)4-(methylsulfonamido)benzoylacetonitrile, 41.0 grams (0.62 mol)malononitrile, and 38 grams (0.496 mol) ammonium acetate in 350 mlabsolute ethanol was heated to reflux with stirring and held at refluxfor two hours. The reaction mixture was cooled to 25° C., poured into250 ml distilled water, and acidified with 43 ml (0.96 mol) 12M HCl. Theresulting precipitate was collected by filtration and washed with waterand ehtanol to yield 60.2 grams (85% yield) of product as a tan powder,m.p.=205°-206° C. All analytical data were consistent with thestructure.

Synthesis of 3-carbamoyl-1,1-dicyano-2-(4-methylsulfonamido)phenylprop-1-ene:

A suspension of 2-(4-methylsulfonamido)phenyl-1,1,3-tricyanoprop-1-ene(2.0 grams , 0.007 mol) in 50 ml concentrated hydrochloric acid solutionwas heated at 70° C. for 2 hours, then allowed to stir at roomtemperature for 20 hours. The resulting tan slurry was filtered througha sintered glass funnel yielding 2.1 grams of crude product. The crudeproduct was slurried at reflux for 20 minutes in 20 ml acetonitrile,collected by filtration, then dried to afford 1.95 grams (92% yield) ofthe amide (m.p.=230° C. dec.) as an off-white powder. All analyticaldata were consistent with the structure.

Synthesis of6-methoxy-2-(4-methylsulfonamido)phenyl-1,1,3-tricyanohexatriene:

Trimethoxypropene (3.0 grams, 0,023 mol) was added in one portion to astirring solution of2-(4-methylsulfonamido)phenyl-1,1,3-tricyanoprop-1-ene (5.0 grams, 0,017mol) in 20 ml acetic anhydride at room temperature. After 20 minutes,the precipitated product was collected by filtration, washed with 20 mlacetic anhydride then dried to afford 3.3 grams (55% yield) of theproduct as a yellow powder (m.p.=170°-172° C. dec.). All analytical datawere consistent with the structure.

Synthesis of Dye 1:

A slurry of 5.72 grams (0.02 mol)2-(4-methylsulfonamidophenyl)-1,1,3-tricyanopropene, 3.13 grams (0.021mol) 4-dimethylaminobenzaldehyde and 30 ml of glacial acetic acid washeated at 130° C. with constant stirring for 30 minutes. The dark purpleproduct mixture was then allowed to cool to room temperature and stirredat room temperature for 16 hours. The precipitated purple crystallineproduct was collected by filtration and washed sequentially withethanol, ether, and ligroin. The weight of dried, crude product was 7.3grams. The crude dye was purified by slurrying in 50 ml refluxingglacial acetic acid with hot filtration. The collected product waswashed with 30 ml glacial acetic acid and dried to afford 5.14 grams(61.5% yield) of pure dye 1, m.p.=224°-225° C. All analytical data wereconsistent with the structure.

Synthesis of Dye 4:

A slurry of 2.37 grams (0.01 mol)2-(4-carboxyphenyl)-1,1,3-tricyanopropene, 1.93 grams (0.011 mol)4-dimethylaminocinnamaldehyde and 30 ml of glacial acetic acid washeated at 130° C. for 30 minutes, cooled to room temperature, andallowed to stir at room temperature for 16 hours. The precipitatedblue-green product was collected and washed sequentially with glacialacetic acid, ether, and ligroin, then dried. The weight of pure dye 4was 2.8 grams (70.9% yield), m.p.=250°-255° C. All analytical data wereconsistent with the dye structure.

Synthesis of Dye 5:

To a mixture of 5.6 grams (0.02 mol)2-(4-methylsulfonamido-1,1,3-tricyanopropene), 1.5 grams (0,015 mol)triethylamine, and 15 ml of ethanol was added with stirring 1.5 grams(0.01 mol) triethylorthoformate. The reaction was stirred at roomtemperature for 2 minutes then heated to reflux. Held at reflux for 2minutes then rapidly cooled to room temperature and allowed to stir atroom temperature for 30 minutes. The salmon-red crystalline product wascollected, washed with ethanol and dried to afford 3.8 grams of crudeproduct. The product was purified by slurrying in ethanol at reflux forone hour, cooling to room temperature, and collecting the crimsoncrystalline product by filtration. The yield of pure dye 5 was 3.3 grams(48.2% yield), m.p.=232°-234° C. All analytical data were consistentwith the structure.

Synthesis of Dye 7:

A slurry of 4.74 grams (0.02 mol)2-(4-carboxyphenyl)-1,1,3-tricyanopropene, 2.64 grams (0.02 mol)trimethoxypropene, 4.4 grams (0.044 mol) triethylamine and 30 ml ofethanol was stirred at room temperature for one hour then heated toreflux for one hour. After allowing to cool to room temperature theproduct mixture was poured into 500 ml of water and 15 ml ofconcentrated hydrochloric acid was added. The precipitated blue-blackproduct was collected and recrystallized by dissolving in 100 ml ofglacial acetic acid at reflux and slowly cooling to room temperaturewith constant stirring. The precipitated product was collected andsequentially washed with acetic acid, ether, and ligroin, then dried toafford 3.12 grams (25.5% yield) of pure dye 7 as a bronzeblack powder,m.p.=277°-279° C. All analytical data were consistent with the dyestructure.

Synthesis of Dye 17:

Triethylamine (0.25 grams, 0025 mol) was added in one portion to astirring solution of 6-methoxy-2-phenyl-1,1,3-tricyanohexatriene (0.5grams, 0,002 mol) and 5-carboxy-2,3-dimethylbenzoxoliump-toluenesulfonate (0.69 grams, 0.002 mol) in 7 ml absolute ethanol. Thesolution turned deep blue instantaneously upon the addition oftriethylamine. The reaction mixture was refluxed for 30 minutes, thenallowed to cool to room temperature and stir for 2 hours. The resultinggreen-blue slurry was filtered, and the collected product was washedwith 10 ml absolute ethanol. The crude dye was slurried at reflux in 10ml absolute ethanol, collected by filtration, then dried to afford 0.55grams (66% yield) of pure dye 17. All analytical data were consistentwith the structure.

Example 1

Dye Wandering and Stain Evaluation

Dyes according to formula (I) were prepared as solid particledispersions by ball-milling according to the following procedure. Water(21.7 ml) and a 6.7% solution of Triton X-200® surfactant (2.65 g) wereplaced in a 60 ml screw-capped bottle. A 1.00 g sample of dye was addedto this solution. Zirconium oxide beads (40 ml, 2 mm diameter) wereadded and the container with the cap tightly secured was placed in amill and the contents milled for four days. The container was removedand the contents added to a 12.5% aqueous gelatin (8.0 g) solution. Thenew mixture was placed on a roller mill for 10 minutes and the resultingmixture was filtered to remove the zirconium oxide beads. The resultingdye dispersion had a particle size mean diameter less than 1.0 μm.

The solid particle dispersions of these dyes were coated on a polyestersupport according to the following procedure. A spreading agent(surfactant 10G®) and a hardener (bis(vinylsulfonylmethyl)ether) wereadded to the dye-gelatin melt prepared as described above. A melt, fromthis mixture was then coated on a poly(ethylene terephthalate) supportto achieve a dye coverage of 0.27 g/m², a gelatin coverage of 1.61 g/m²,a spreading agent level of 0.097 g/m², and a hardener level of 0.016g/m². The absorbance of the dye dispersion was measured with aspectrophotometer. Identical elements were subjected to a 5 minutedistilled water wash (2-3 gal/min flow rate), and to Kodak E-6®Processing (which is described in British Journal of Photography Annual,1977, pp. 194-97) and the absorbance was measured for each. The resultsare shown in Table I.

                  TABLE I                                                         ______________________________________                                                                 D-max after                                                                            D-max after                                 DYE    λ-max                                                                           D-max    Water Wash                                                                             E-6 ® Processing                        ______________________________________                                         1     534 nm   0.90     0.90     0.00                                         4     567 nm   1.40     1.37     0.00                                         5     566 nm   1.41     1.49     0.00                                         9     433 nm   1.45     1.46     0.00                                        15     651 nm   1.48     1.49     0.04                                        16     453 nm   2.52     2.67     0.00                                        17     622 nm   1.49     1.49     0.04                                        20     442 nm   1.10     1.06     0.00                                        21     537 nm   0.94     0.94     0.00                                        ______________________________________                                    

These results show that the dyes of formula (I) are not affected by thewater wash, indicating no wandering at coating pH, but are fullysolubilized for removal and/or decolorization during photographicprocessing.

Example 2

Covering Power

Solid particle dispersions of dyes 8, 14, 16, and 20 and comparison dyesA, B, C, D, and E were prepared and coated on a polyester supportsimilarly to the dyes of the invention as described in Example 1. Thesecomparison dyes are analogous to dyes 8, 14, 16, and 20 of theinvention, with the substitution of a pyrazolone or benzoylacetonitrileketomethylene nucleus in place of the tricyanopropene nucleus of dyes 8,14, 16, and 20, as illustrated below. The absorbance of the dyedispersions were measured with a spectrophotometer, and the coveringpower (C.P.) was determined for each dye. The covering power of a dye ina solid particle dispersion coating is defined as the optical density ata chosen λmax divided by the coated dye laydown in mg/ft². For thisinvestigation, the C.P. values of the dyes were compared based on theoptical density at their relative λmax's (Dmax). The following resultsshown in Table II were achieved:

                  TABLE II                                                        ______________________________________                                                             Dye Coverage                                             Dye     Dmax         (mg/ft.sup.2)                                                                             C.P.                                         ______________________________________                                        8       1.2          15          0.077                                        A        0.65        12          0.054                                        14      2.1          25          0.084                                        B       1.5          25          0.060                                        C       1.8          25          0.073                                        16      2.5          25          0.100                                        D       1.2          25          0.049                                        20      1.1          25          0.044                                        E        0.83        25          0.033                                        ______________________________________                                    

The structures of the dyes of Table II are shown below: ##STR40##

The above results demonstrates that the dyes of the invention havegreater covering power than their prior art analogues.

The invention has been described in detail with reference to preferredembodiments thereof. It should be understood, however, that variationsand modifications can be made within the spirit and scope of theinvention.

What is claimed is:
 1. A dye having the formula: ##STR41## wherein: D isselected from the group consisting of ##STR42## and ketomethylenenuclei; E¹ and E² are each independently electron withdrawing groups;R¹and R⁶ are each independently R or NHR, where R is aryl or substitutedaryl with from 6 to 14 carbon atoms, the substituents being a halogen,alkoxy, ester, amido, acyl, alkylamino, carboxy, or sulfonamido; R⁷ ishydrogen, substituted or unsubstituted alkyl of from 1 to 6 carbon atomsor substituted or unsubstituted aryl of from 6 to 14 carbon atoms,wherein the substituents are a halogen, alkoxy, ester, amido, acyl,alkylamino, carboxy, or sulfonamido; R⁵ is substituted or unsubstitutedalkyl of from 1 to 15 carbon atoms wherein the substituents are ahalogen, alkoxy, ester, amido, acyl, alkylamino, carboxy, orsulfonamido; Z represents the atoms necessary to complete a substitutedor unsubstituted thiazole, selenazole, oxazole, imidazole, indolebenzothiazole, benzoselenazole, benzoxazole, benzimidazole, benzindole,naphthothiazole, naphthoselenazole, naphthoxazole, or naphthimidazole,wherein the substituents are alkyl of from 1 to 10 carbon atoms, alkoxyof from 1 to 8 carbon atoms, halogen, or aryl of 6 to 20 carbon atoms;M⁺ is a cation; L¹ through L⁷ are each independently substituted orunsubstituted methine wherein the substituents are substituted orunsubstituted alkyl of from 1 to 6 carbon atoms or substituted orunsubstituted aryl of from 6 to 14 carbon atoms in which thesubstituents are a halogen, alkoxy, ester, amido, acyl, alkylamino,carboxy, or sulfonamido; m is 0, 1, 2, or 3; n is 0 or 1; q is 0, 1, 2,or 3; and wherein at least one of R¹ or D has an aryl substituted with acarboxy or sulfonamido substituent.
 2. A dye according to claim 1wherein D is ##STR43##
 3. A dye according to claim 1 wherein D is##STR44##
 4. A dye according to claim 1 wherein D is ketomethylenenucleus selected from the group consisting of benzoyl aceonitrile,2-pyrazolin-5-one, pyrazolindione, barbituric acid nuclei, rhodanine,indanedione, isoxazolinone, benzofuranone, chromandione,cyclohexanedione, dioxanedione, furanone, isoxazolidindione, pyrandione,and pyrrolinone.
 5. A dye according to claim 1 wherein D is ##STR45## 6.A dye according to claim 5 wherein Z represents the atoms necessary tocomplete a substituted or unsubstituted benzoxazole nucleus.
 7. A dyeaccording to claim 1 wherein E¹ and E² are selected from the groupconsisting of cyano, acyl, aminocarbonyl, and alkoxycarbonyl.
 8. A dyeaccording to claim 1 wherein E¹ and E² are cyano.